Fungicidal pyrimidinyloxyphenyl-3-methoxy propenoates

ABSTRACT

Fungicidal compounds having the formula (I): ##STR1## in which any two of K, L and M are nitrogen and the other is CH; and X is an optionally substituted 3- to 6-membered heterocyclic ring containing at least one trivalent nitrogen atom by which it is attached to the central pyrimidine ring.

This is a continuation of application Ser. No. 07/616,454, filed Nov.20, 1990, now U.S. Pat. No. 5,179,098.

This invention relates to derivatives of propenoic acid useful asfungicides, to processes for preparing them, to fungicidal compositionscontaining them, and to methods of using them to combat fungi,especially fungal infections of plants.

According to the present invention there are provided compounds havingthe formula (I): ##STR2## in which any two of K, L and M are nitrogenand the other is CH; and X is an optionally substituted 3- to 6-memberedheterocyclic ring containing at least one trivalent nitrogen atom bywhich it is attached to the central pyrimidine ring.

Because of the unsymmetrically substituted double bond of the propenoategroup, the compounds of the invention may be obtained in the form ofmixtures of (E)-and (Z)-geometric isomers. However, these mixtures canbe separated into individual isomers, and this invention embraces suchisomers and mixtures thereof in all proportions including those whichconsist substantially of the (Z)-isomer and those which consistsubstantially of the (E)-isomer

The (E)-isomer, in which the groups --CO₂ CH₃ and --OCH₃ are on oppositesides of the olefinic bond of the propenoate group, are the morefungicidally active and form a preferred embodiment of the invention.##STR3## in formula (I) is a pyrimidine ring. Of particular interest isthe pyrimidine ring in which K and L are both nitrogen and M is CH.

The group X is an optionally substituted 3- to 6-membered heterocyclicring containing at least one trivalent nitrogen atom by which it isattached to the central pyrimidine ring. The following are examples ofsuitable rings: pyrrole, imidazole, pyrazole, 1,2,4-triazole,1,2,3-triazole, 1,3,4-triazole, pyridone, pyrimidinone, pyrazinone,pyridazinone, 1,2,4-triazinone 1,3,5-triazinone, indole, aziridine,azetidine, pyrrolidine, piperidine and morpholine.

As the nitrogen atom by which X is attached to the central pyrimidinering is trivalent, X does not include such aromatic nitrogen-containingrings as pyridine, pyrimidine, etc. without modification by, forexample, the inclusion of an oxo substituent to form a pyridone orpyrimidone ring.

Thus X is a ring ##STR4## wherein R is a 2- to 5-membered, saturated orunsaturated chain in which the members are carbon atoms and optionallyone or more heteroatoms such as nitrogen, oxygen or sulphur; Z is asubstituent of the type described below; m is 0 or an integer of from 1to 5 according to the size and composition of the chain R and as valencyallows; and, when m is 2 or more, the substituents Z may be the same ordifferent.

Typically R is a 2- to 5-membered, saturated or unsaturated carbon chainor a 4- to 5-membered, saturated or unsaturated chain in which themembers are carbon atoms and one or two nitrogen atoms or an oxygenatom. In one particular embodiment, R is a 5-membered, unsaturated chainin which the members are carbon atoms and one or two nitrogen atoms, and(Z)_(m) includes an oxo group attached to a carbon atom not linked toanother atom by an unsaturated bond.

Typical optional substituents (Z) of the heterocyclic ring X arehalogen, C₁₋₄ alkyl, C₃₋₆ cycloalkyl, C₂₋₄ alkenyl, C₂₋₄ alkynyl, C₂₋₄alkenyloxy, C₂₋₄ alkynyloxy, phenyl, benzyloxy, cyano, isocyano,isothiocyanato, nitro, oxo, NR¹ R², NHCOR¹, NHCONR¹ R², NHSO₂ R¹, OR¹,OCOR¹, OSO₂ R¹, SR¹, SOR¹, SO₂ R¹, COR¹, CR¹ =NOR², CO₂ R¹, CONR¹ R²,CSNR¹ R². When substituents are ortho to one another, they may join toform a 5- or 6-membered aliphatic or aromatic ring optionally containingone or more oxygen, sulphur or nitrogen atoms and optionally substitutedwith one or more of the substituents recited for X above. Suitably theyjoin to form a benzene ring. Examples of the ring X where itssubstituents join to form a benzene ring are benzimidazole,benzotriazole and benzotriazinone. R¹ and R² are independently hydrogen,C₁₋₄ alkyl or phenyl. The aliphatic moieties of any of the substituentsmay themselves be substituted with one or more of halogen, cyano, OR¹ orOCOR¹ and the phenyl moieties of any of the substituents may themselvesbe substituted with one or more of halogen C₁₋₄ alkyl, C₁₋₄ alkoxy,nitro or cyano.

Alkyl groups contain from 1 to 4 carbon atoms and may be in the form ofstraight or branched chains. Examples are methyl, ethyl, iso-propyl,n-butyl and t-butyl. Substituted alkyl groups include C₁₋₄ haloalkylgroups and, in particular, trifluoromethyl groups. Cycloalkyl groupscontain from 3 to 6 carbon atoms and include cyclopropyl and cyclohexyl.

Alkenyl and alkynyl groups contain from 2 to 4 carbon atoms and may bein the form of straight or branched chains. Examples are ethenyl, allyl,methylallyl and propargyl.

Halogen is typically fluorine, chlorine or bromine.

Aliphatic moieties which may be substituted include, in particular, C₁₋₄alkyl groups.

In one aspect the invention provides a compound of the formula (I.1).##STR5## in which Y is H, C₁₋₄ alkyl (especially methyl) ortrifluoromethyl.

The invention is illustrated by the compounds listed in Tables I to IIIwhich follow. Throughout these Tables the methyl 3-methoxypropenoategroup has the (E)-configuration.

                  TABLE I                                                         ______________________________________                                         ##STR6##                                                                     Compound                                                                      No.     X                 M.pt. (°C.)                                                                      δ.sup.+                             ______________________________________                                                 ##STR7##                                                             2                                                                                      ##STR8##                                                             3                                                                                      ##STR9##                                                             4                                                                                      ##STR10##                                                            5                                                                                      ##STR11##                                                            6                                                                                      ##STR12##                                                            7                                                                                      ##STR13##                                                            8                                                                                      ##STR14##        Gum       7.45                                      9                                                                                      ##STR15##                                                            10                                                                                     ##STR16##                                                            11                                                                                     ##STR17##                                                            12                                                                                     ##STR18##                                                            13                                                                                     ##STR19##                                                            14                                                                                     ##STR20##                                                            15                                                                                     ##STR21##                                                            16                                                                                     ##STR22##                                                            17                                                                                     ##STR23##        Glass     7.47                                      18                                                                                     ##STR24##        100-102   7.47                                      19                                                                                     ##STR25##                                                            20                                                                                     ##STR26##                                                            21                                                                                     ##STR27##                                                            22                                                                                     ##STR28##                                                            23                                                                                     ##STR29##                                                            24                                                                                     ##STR30##                                                            25                                                                                     ##STR31##                                                            26                                                                                     ##STR32##                                                            27                                                                                     ##STR33##                                                            28                                                                                     ##STR34##                                                            29                                                                                     ##STR35##                                                            30                                                                                     ##STR36##        139-141° C.                                                                      7.48                                      31                                                                                     ##STR37##        130-131° C.                                                                      7.48                                      ______________________________________                                    

                  TABLE II                                                        ______________________________________                                         ##STR38##                                                                    Compound                                                                      No.       X                M.pt. (°C.)                                                                      δ.sup.+                            ______________________________________                                                   ##STR39##                                                          2                                                                                        ##STR40##                                                          3                                                                                        ##STR41##                                                          4                                                                                        ##STR42##                                                          5                                                                                        ##STR43##                                                          6                                                                                        ##STR44##                                                          7                                                                                        ##STR45##                                                          8                                                                                        ##STR46##                                                          9                                                                                        ##STR47##                                                          10                                                                                       ##STR48##                                                          11                                                                                       ##STR49##                                                          12                                                                                       ##STR50##                                                          13                                                                                       ##STR51##                                                          14                                                                                       ##STR52##                                                          15                                                                                       ##STR53##                                                          16                                                                                       ##STR54##                                                          17                                                                                       ##STR55##                                                          18                                                                                       ##STR56##                                                          19                                                                                       ##STR57##                                                          20                                                                                       ##STR58##                                                          21                                                                                       ##STR59##                                                          22                                                                                       ##STR60##                                                          23                                                                                       ##STR61##                                                          24                                                                                       ##STR62##                                                          25                                                                                       ##STR63##                                                          26                                                                                       ##STR64##                                                          27                                                                                       ##STR65##                                                          28                                                                                       ##STR66##                                                          29                                                                                       ##STR67##                                                          30                                                                                       ##STR68##                                                          31                                                                                       ##STR69##                                                          ______________________________________                                    

                  TABLE III                                                       ______________________________________                                         ##STR70##                                                                    Compound                                                                      No.       X                M.pt. (°C.)                                                                      δ.sup.+                            ______________________________________                                                   ##STR71##                                                          2                                                                                        ##STR72##                                                          3                                                                                        ##STR73##                                                          4                                                                                        ##STR74##                                                          5                                                                                        ##STR75##                                                          6                                                                                        ##STR76##                                                          7                                                                                        ##STR77##                                                          8                                                                                        ##STR78##                                                          9                                                                                        ##STR79##                                                          10                                                                                       ##STR80##                                                          11                                                                                       ##STR81##                                                          12                                                                                       ##STR82##                                                          13                                                                                       ##STR83##                                                          14                                                                                       ##STR84##                                                          15                                                                                       ##STR85##                                                          16                                                                                       ##STR86##                                                          17                                                                                       ##STR87##                                                          18                                                                                       ##STR88##                                                          19                                                                                       ##STR89##                                                          20                                                                                       ##STR90##                                                          21                                                                                       ##STR91##                                                          22                                                                                       ##STR92##                                                          23                                                                                       ##STR93##                                                          24                                                                                       ##STR94##                                                          25                                                                                       ##STR95##                                                          26                                                                                       ##STR96##                                                          27                                                                                       ##STR97##                                                          28                                                                                       ##STR98##                                                          29                                                                                       ##STR99##                                                          30                                                                                       ##STR100##                                                         31                                                                                       ##STR101##                                                         ______________________________________                                         .sup.+ Chemical shift of singlet from olefinic proton on                      β-methoxypropenoate group (ppm from tetramethylsilane).             

The compounds of the invention of formula (I) [equivalent to (IA) when Wis the group CH₃ O₂ C.C═CH.OCH₃ ] can be prepared by the steps shown inSchemes I and II. In these Schemes the terms K, L, and M are as definedabove; X' is either X, or is a group which can be converted into X bymethods described in the chemical literature, wherein X is as describedabove; W is CH₃ O₂ C.C═CH.OCH₃ or a group that can be transformed intoCH₃ O₂ C.C═CH.OCH₃ using methods previously described such as inEP-A-0242081; Z¹ and Z² are leaving groups (such as halogen or CH₃ SO₂--); and T is hydrogen or a metal (such as sodium). The reactions shownin Schemes I and II are performed either in a suitable solvent orwithout a solvent, and at a suitable temperature.

Thus compounds of the invention of formula (IA) can be prepared bytreatment of substituted pyrimidines of general formula (III) withphenols of formula (II) (wherein W is as defined above and T ishydrogen) in the presence of a base (such as potassium carbonate)(Scheme I).

Alternatively, compounds of formula (IA) can be prepared by treatment ofsubstituted pyrimidines of general formula (III) with phenolate salts offormula (II) (wherein W is as defined above and T is a metal, such assodium) (Scheme I). ##STR102##

Alternatively, the compounds of the invention of formula (I) (equivalentto (IA) when W is the group CH₃ O₂ C.C═CH.OCH₃) can be prepared by thesteps shown in Scheme II.

Thus compounds of the invention of formula (IA) can be prepared bytreatment of substituted pyrimidines of general formula (IV) withheterocycles of general formula (V) (wherein X' is as defined above andT is hydrogen) in the presence of a base (such as potassium carbonate).

Alternatively, compounds of the invention of formula (IA) can beprepared by treatment of substituted pyrimidines of general formula (IV)with salts of formula (V) (wherein X' is as defined above and T is ametal, such as sodium).

Substituted pyrimidines of general formula (IV) can be prepared bytreatment of pyrimidines of general formula (VI) with phenols of generalformula (II) (wherein W is as defined above and T is hydrogen) in thepresence of a base (such as potassium carbonate). ##STR103##

Alternatively, substituted pyrimidines of general formula (IV) can beprepared by treatment of pyrimidines of general formula (VI) withphenolate salts of general formula (II) (wherein W is as defined aboveand T is a metal, such as sodium).

The last stage of the synthesis of the compounds of the invention maytherefore be one of the following:

(i) construction of the group CH₃ O₂ C.C═CH.OCH₃ [in which case thegroup W in the compounds (II), (IV) and (IA) represents an appropriateprecursor to the group CH₃ O₂ C.C═CH.OCH₃ during the coupling reactionsshown in Schemes I and II]; or

(ii) the coupling reaction shown in Scheme I or the second couplingreaction shown in Scheme II [in which case the group W in theintermediates (II) or (IV) represents the group CH₃ O₂ C.C═CH.OCH₃ ]; or

(iii) construction of the group X from the group X' (this could be themodification of a substituent on the group X').

Pyrimidines of formulae (III) and (VI) and heterocycles of formula (V)can be prepared by standard methods described in the chemicalliterature. Compounds of formula (II) can either be prepared by standardmethods described in the chemical literature, or when W is CH₃ O₂C.C═CH.OCH₃, can be prepared by methods described in EP-A-0242081.

In a further aspect, the invention provides processes as hereindescribed for preparing the compounds of the invention.

The compounds of the invention are active fungicides and may be used tocontrol one or more of the following pathogens:

The compounds are active fungicides and may be used to control one ormore of the following pathogens: Pyricularia oryzae on rice. Pucciniarecondita, Puccinia striiformis and other rusts on wheat, Pucciniahordei, Puccinia striiformis and other rusts on barley, and rusts onother hosts e.g. coffee, pears, apples, peanuts, vegetables andornamental plants. Erysiphe graminis (powdery mildew) on barley andwheat and other powdery mildews on various hosts such as Sphaerothecamacularis on hops, Sphaerotheca fuliginea on cucurbits (e.g. cucumber),Podosphaera leucotricha on apple and Uncinula necator on vines.Helminthosporium spp., Rhynchosporium spp., Septoria spp., Pyrenophoraspp., Pseudocercosporella herpotrichoides and Gaeumannomyces graminis oncereals. Cercospora arachidicola and Cercosporidium personata on peanutsand other Cercospora species on other hosts, for example, sugar beet,bananas, soya beans and rice. Botrytis cinerea (grey mould) on tomatoes,strawberries, vegetables, vines and other hosts. Alternaria spp. onvegetables (e.g. cucumber), oil-seed rape, apples, tomatoes and otherhosts. Venturia inaequalis (scab) on apples. Plasmopara viticola onvines. Other downy mildews such as Bremia lactucae on lettuce,Peronospora spp. on soybeans, tobacco, onions and other hosts,Pseudoperonospora humuli on hops and Pseudoperonospora cubensis oncucurbits. Phytophthora infestans on potatoes and tomatoes and otherPhytophthora spp. on vegetables, strawberries, avocado, pepper,ornamentals, tobacco, cocoa and other hosts. Thanatephorus cucumeris onrice and other Phizoctonia species on various hosts such as wheat andbarley, vegetables, cotton and turf.

Some of the compounds shown a broad range of activities against fungi invitro. They may also have activity against various post-harvest diseasesof fruit (e.g. Penicillium digitatum and italicum and Trichoderma virideon oranges, Gloeosporium musarum on bananas and Botrytis cinerea ongrapes).

Further, some of the compounds may be active as seed dressings againstpathogens including Fusarium spp., Septoria spp., Tilletia spp., (bunt,a seed-borne disease of wheat), Ustilago spp. and Helminthosporium spp.on cereals, Rhizoctonia solani on cotton and Pyricularia oryzae on rice.

The compounds may move acropetally/locally in plant tissue. Moreover,the compounds may be volatile enough to be active in the vapour phaseagainst fungi on the plant.

The invention therefore provides a method of combating fungi whichcomprises applying to a plant, to a seed of a plant or to the locus ofthe plant or seed a fungicidally effective amount of a compound ashereinbefore defined, or a composition containing the same.

The compounds may be used directly for agricultural purposes but aremore conveniently formulated into compositions using a carrier ordiluent. The invention thus provides fungicidal compositions comprisinga compound as hereinbefore defined and an acceptable carrier or diluenttherefor.

The compounds can be applied in a number of ways. For example, they canbe applied, formulated or unformulated, directly to the foliage of aplant, to seeds or to other medium in which plants are growing or are tobe planted, or they can be sprayed on, dusted on or applied as a creamor paste formulation, or they can be applied as a vapour or as slowrelease granules.

Application can be to any part of the plant including the foliage,stems, branches or roots, or to soil surrounding the roots, or to theseed before it is planted, or to the soil generally, to paddy water orto hydroponic culture systems. The invention compounds may also beinjected into plants or sprayed onto vegetation using electrodynamicspraying techniques or other low volume methods.

The term "plant" as used herein includes seedlings, bushes and trees.Furthermore, the fungicidal method of the invention includespreventative, protectant, prophylactic and eradicant treatments.

The compounds are preferably used for agricultural and horticulturalpurposes in the form of a composition. The type of composition used inany instance will depend upon the particular purpose envisaged.

The compositions may be in the form of dustable powders or granulescomprising the active ingredient (invention compound) and a soliddiluent or carrier, for example, fillers such as kaolin, bentonite,kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia,fuller's earth, gypsum, diatomaceous earth and china clay. Such granulescan be preformed granules suitable for application to the soil withoutfurther treatment. These granules can be made either by impregnatingpellets of filler with the active ingredient or by pelleting a mixtureof the active ingredient and powdered filler. Compositions for dressingseed may include an agent (for example, a mineral oil) for assisting theadhesion of the composition to the seed; alternatively the activeingredient can be formulated for seed dressing purposes using an organicsolvent (for example, N-methylpyrrolidone, propylene glycol ordimethylformamide). The compositions may also be in the form of wettablepowders or water dispersible granules comprising wetting or dispersingagents to facilitate the dispersion in liquids. The powders and granulesmay also contain fillers and suspending agents.

Emulsifiable concentrates or emulsions may be prepared by dissolving theactive ingredient in an organic solvent optionally containing a wettingor emulsifying agent and then adding the mixture to water which may alsocontain a wetting or emulsifying agent. Suitable organic solvents arearomatic solvents such as alkylbenzenes and alkylnaphthalenes, ketonessuch as cyclohexanone and methylcyclohexanone, chlorinated hydrocarbonssuch as chlorobenzene and trichlorethane, and alcohols such as benzylalcohol, furfuryl alcohol, butanol and glycol ethers.

Suspension concentrates of largely insoluble solids may be prepared byball or bead milling with a dispersing agent with a suspending agentincluded to stop the solid settling.

Compositions to be used as sprays may be in the form of aerosols whereinthe formulation is held in a container under pressure of a propellant,e.g. fluorotrichloromethane or dichlorodifluoromethane.

The invention compounds can be mixed in the dry state with a pyrotechnicmixture to form a composition suitable for generating in enclosed spacesa smoke containing the compounds.

Alternatively, the compounds may be used in micro-encapsulated form.They may also be formulated in biodegradable polymeric formulations toobtain a slow, controlled release of the active substance.

By including suitable additives, for example additives for improving thedistribution, adhesive power and resistance to rain on treated surfaces,the different compositions can be better adapted for various utilities.

The invention compounds can be used as mixtures with fertilisers (e.g.nitrogen-, potassium- or phosphorus-containing fertilisers).Compositions comprising only granules of fertiliser incorporating, forexample coated with, the compound are preferred. Such granules suitablycontain up to 25% by weight of the compound. The invention thereforealso provides a fertiliser composition comprising a fertiliser and thecompound of general formula (I) or a salt or metal complex thereof.

Wettable powders, emulsifiable concentrates and suspension concentrateswill normally contain surfactants, e.g. a wetting agent, dispersingagent, emulsifying agent or suspending agent. These agents can becationic, anionic or non-ionic agents.

Suitable cationic agents are quaternary ammonium compounds, for example,cetyltrimethylammonium bromide. Suitable anionic agents are soaps, saltsof aliphatic monoesters of sulphuric acid (for example, sodium laurylsulphate), and salts of sulphonated aromatic compounds (for example,sodium dodecylbenzenesulphonate, sodium, calcium or ammoniumlignosulphonate, butylnaphthalene sulphonate, and a mixture of sodiumdiisopropyl- and triisopropyl-naphthalene sulphonates).

Suitable non-ionic agents are the condensation products of ethyleneoxide with fatty alcohols such as oleyl or cetyl alcohol, or with alkylphenols such as octyl- or nonylphenol and octylcresol. Other non-ionicagents are the partial esters derived from long chain fatty acids andhexitol anhydrides, the condensation products of the said partial esterswith ethylene oxide, and the lecithins. Suitable suspending agents arehydrophilic colloids (for example, polyvinylpyrrolidone and sodiumcarboxymethylcellulose), and swelling clays such as bentonite orattapulgite.

Compositions for use as aqueous dispersions or emulsions are generallysupplied in the form of a concentrate containing a high proportion ofthe active ingredient, the concentrate being diluted with water beforeuse. These concentrates should preferably be able to withstand storagefor prolonged periods and after such storage be capable of dilution withwater in order to form aqueous preparations which remain homogeneous fora sufficient time to enable them to be applied by conventional sprayequipment. The concentrates may conveniently contain up to 95%, suitably10-85%, for example 25-60%, by weight of the active ingredient. Afterdilution to form aqueous preparations, such preparations may containvarying amounts of the active ingredient depending upon the intendedpurpose, but an aqueous preparation containing 0.0005% or 0.01% to 10%by weight of active ingredient may be used.

The compositions of this invention may contain other compounds havingbiological activity, e.g. compounds having similar or complementaryfungicidal activity or which possess plant growth regulating, herbicidalor insecticidal activity.

A fungicidal compound which may be present in the composition of theinvention may be one which is capable of combating ear diseases ofcereals (e.g. wheat) such as Septoria, Gibberella and Helminthosporiumspp., seed and soil-borne diseases and downy and powdery mildews ongrapes and powdery mildew and scab on apple, etc. By including anotherfungicide, the composition can have a broader spectrum of activity thanthe compound of general formula (I) alone. Further the other fungicidecan have a synergistic effect on the fungicidal activity of the compoundof general formula (I). Examples of fungicidal compounds which may beincluded in the composition of the invention are(RS)-1-aminopropylphosphonic acid,(RS)-4-(4-chlorophenyl)-2-phenyl-2-(1H-1,2,4-triazol-1-yl-methyl)butyronitrile,(Z)-N-but-2-enyloxymethyl-2-chloro-2',6'-diethylacetanilide,1-(2-cyano-2-methoxyiminoacetyl)-3-ethyl urea,1-[(2RS,4RS;2RS,4RS)-4-bromo-2-(2,4-dichlorophenyl)tetrahydrofurfuryl]-1H-1,2,4-triazole,3-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)quinazolin-4(3H)-one,3-chloro-4-[4-methyl-2-(1H-1,2,4-triazol-1-methyl)-1,3-dioxolan-2-yl]phenyl-4-chlorophenyl ether,4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethylbenzimidazole-1-sulphonamide,5-ethyl-5,8-dihydro-8-oxo(1,3)-dioxolo(4,5-g)quinoline-7-carboxylicacid, α-[N-(3-chloro-2,6-xylyl)-2-methoxyacetamido]-γ-butyrolactone,aldimorph, anilazine, benalaxyl, benomyl, biloxazol, binapacryl,bitertanol, blasticidin S, bupirimate, buthiobate, captafol, captan,carbendazim, carboxin, chlorbenz-thiazone, chloroneb, chlorothalonil,chlorozolinate, copper containing compounds such as copper oxychloride,copper sulphate and Bordeaux mixture, cycloheximide, cymoxanil,cyproconazole, cyprofuram, di-2-pyridyl disulphide 1,1'-dioxide,dichlofluanid, dichlone, diclobutrazol, diclomezine, dicloran,difenoconazole, dimethamorph, dimethirimol, diniconazole, dinocap,ditalimfos, dithianon, dodemorph, dodine, edifenphos, etaconazole,ethirimol, ethyl(Z)-N-benzyl-N-([methyl(methylthioethylideneamino-oxycarbonyl)amino]thio)-β-alaninate,etridiazole, fenapanil, fenarimol, fenfuram, fenpiclonil, fenpropidin,fenpropimorph, fentin acetate, fentin hydroxide, flutolanil, flutriafol,flusilazole, folpet, fosetyl-aluminium, fuberidazole, furalaxyl,furconazole-cis, guazatine, hexaconazole, hydroxyisoxazole, imazalil,imibenconazole, iprobenfos, iprodione, isoprothiolane, kasugamycin,mancozeb, maneb, mepanipyrim, mepronil, metalaxyl, methfuroxam,metsulfovax, myclobutanil,N-(4-methyl-6-prop-1-ynylpyrimidin-2-yl)aniline, neoasozin, nickeldimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace,organomercury compounds, oxadixyl, oxycarboxin, pefurazoate,penconazole, pencycuron, phenazin oxide, phthalide, polyoxin D, polyram,probenazole, prochloraz, procymidone, propamocarb, propiconazole,propineb, prothiocarb, pyrazophos, pyrifenox, pyroquilon, pyroxyfur,pyrrolnitrin, quinomethionate, quintozene, SSF-109, streptomycin,sulphur, tebuconazole, techlofthalam, tecnazene, tetra-conazole,thiabendazole, thicyofen, thiophanate-methyl, thiram, tolclofos-methyl,triacetate salt of 1,1'-iminodi(octa-methylene)diguanidine, triadimefon,triadimenol, triazbutyl, tricyclazole, tridemorph, triforine,validamycin A, vinclozolin, zarilamid and zineb. The compounds ofgeneral formula (I) can be mixed with soil, peat or other rooting mediafor the protection of plants against seed-borne, soil-borne or foliarfungal diseases.

Suitable insecticides which may be incorporated in the composition ofthe invention include buprofezin, carbaryl, carbofuran, carbosulfan,chlorpyrifos, cycloprothrin, demeton-s-methyl, diazinon, dimethoate,ethofenprox, fenitrothion, fenobucarb, fenthion, formothion, isoprocarb,isoxathion, monocrotophos, phenthoate, pirimicarb, propaphos and XMC.

Plant growth regulating compounds are compounds which control weeds orseedhead, formation, or selectively control the growth of less desirableplants (e.g. grasses).

Examples of suitable plant growth regulating compounds for use with theinvention compounds are 3,6-dichloropicolinic acid,1-(4-chlorophenyl)-4,6-dimethyl-2-oxo-1,2-dihydropyridine-3-carboxylicacid, methyl-3,6-dichloroanisate, abscisic acid, asulam,benzoylprop-ethyl, carbetamide, daminozide, difenzoquat, dikegulac,ethephon, fenpentezol, fluoridamid, glyphosate, glyphosine,hydroxybenzonitriles (e.g. bromoxynil), inabenfide, isopyrimol, longchain fatty alcohols and acids, maleic hydrazide, mefluidide,morphactins (e.g. chlorfluoroecol), paclobutrazol, phenoxyacetic acids(e.g. 2,4-D or MCPA), substituted benzoic acid (e.g. triiodobenzoicacid), substituted quaternary ammonium and phosphonium compounds (e.g.chloromequat, chlorphonium or mepiquatchloride), tecnazene, the auxins(e.g. indoleacetic acid, indolebutyric acid, naphthylacetic acid ornaphthoxyacetic acid), the cytokinins (e.g. benzimidazole,benzyladenine, benzylaminopurine, diphenylurea or kinetin), thegibberellins (e.g. GA₃, GA₄ or GA₇) and triapenthenol.

The following Examples illustrate the invention. In the Examples, theterm `ether` refers to diethyl ether, anhydrous magnesium sulphate wasused to dry solutions, and solutions were concentrated under reducedpressure. Reactions involving air- or water-sensitive intermediates wereperformed under an atmosphere of nitrogen and solvents were dried beforeuse, where appropriate. Unless otherwise stated, chromatography wasperformed on a column of silica gel as the stationary phase. NMR dataare selective; no attempt is made to list every absorption in all cases.¹ H NMR spectra were recorded using CDCl₃ -solutions. The followingabbreviations are used:

DMF=N,N-dimethylformamide

NMR=nuclear magnetic resonance

IR=infrared

s=singlet

d=doublet

m=multiplet

t=triplet

mp=melting point

ppm=parts per million.

EXAMPLE 1

This Example illustrates the preparation of (E)-methyl2-[2-(6-(3-methylpyridin-2-onyl)-pyrimidin-4-yloxy)phenyl]-3-methoxypropenoate(Compound No. 17 of Table I).

To a solution of 4,6-dichloropyrimidine (0.76 g, 5.10 mmol) in dry DMF(4 ml) at 0° C. was added anhydrous potassium carbonate (0.70 g, 5.10mmol). A solution of (E)-methyl 2-(2-hydroxyphenyl)-3-methoxypropenoate(0.53 g, 2.55 mmol) in dry DMF (2 ml) was then added dropwise withstirring. After the addition was complete, the reaction mixture wasallowed to warm to room temperature and stirring continued over theweekend. The reaction mixture was then diluted with water (15 ml) andextracted with ether (3×20 ml). The combined ether extracts were washedwith brine and dried. Evaporation afforded a brown liquid (1.10 g) whichwas chromatographed (eluent ether:n-hexane, 3:2) to give (E)-methyl2-[2-(6-chloropyrimidin-4-yloxy)phenyl]-3-methoxy-propenoate as a thick,pale yellow oil (0.58, 71%) which crystallised on standing.

Recrystallisation from ether/dichloromethane(trace)/n-hexane at -78° C.gave the product as a white powder (0.25 g), mp 94°-5° C. In a separatepreparation, 15 g of product was obtained from 4,5-dichloropyrimidine(15.90 g), (E)-methyl 2-(2-hydroxyphenyl)-3-methoxy-propenoate (14.80 g)and anhydrous potassium carbonate (19.64 g).

To a suspension of (E)-Methyl2-[2-(6-chloropyrimidin-4-yloxy)phenyl]-3-methoxypropenoate (0.50 g,1.56 mmol) in dry toluene (25 ml) were added 3-methyl-2-pyridone (0.17g, 1.72 mmol) and silver carbonate (0.47 g, 1.72 mmol). The mixture wasrefluxed overnight and then further amounts of 3-methyl-2-pyridone (0.08g) and silver carbonate (0.23 g) were added. The resulting mixture washeated at reflux overnight, cooled and filtered through a plug ofcelite. The celite was washed through with toluene (2×20 ml) and thecombined solutions evaporated to give a brown oil (0.75 g).Chromatography on silicagel (eluent ethyl acetate:n-hexane, 3:1)afforded the title compound as a pale yellow foam which set to a glass(0.19 g, 31%); IR max. 1664 cm⁻¹, ¹ H NMR (CDCl₃) δ2.19(3H,s);3.62(3H,s); 3.73(3H,s); 6.24(1H,t); 7.20-7.51 (5H,m); 7.47(1H,s);7.77(1H,s); 7.99(1H,d); 8.73(1H,s) ppm.

Mass spectrum m/e 393 (M⁺).

EXAMPLE 2

This Example illustrates the preparation of (E)-methyl2-[2-(6-(benztriazol-1-yl)pyrimidin-4-yloxy)phenyl]-3-methoxypropenoate(Compound No. 30 of Table I).

A mixture containing benzotriazole (0.262 g, 2.2 mmol) and anhydrouspotassium carbonate (0.30 g, 2.2 mmol) in dry DMF (5 ml) was heated at100° C. for one hour under an atmosphere of nitrogen. The resulting greymixture was cooled to -40° C. and a solution of (E)-methyl2-[2-(6-chloropyrimidin-4-yloxy)phenyl]-3-methoxypropenoate (0.641 g, 2mmol) in dry DMF (5 ml) was added drop-wise over ten minutes. Thereaction mixture was stirred for a further ten minutes, allowed to warmto room temperature and then stirred for 41/4 hours. The reactionmixture was filtered and the filtrate diluted with water and extractedwith ether (×4). The combined ether extracts were washed with water,dried and evaporated to give an orange residue (0.40 g). Chromatographyon silicagel (eluent acetone:hexane, 1:4) afforded the title compound asa yellow solid (0.03 g); m.p. 139°-141° C.; IR max. 1709, 1632 cm⁻¹ ; ¹H NMR (CDCl₃) δ3.61(3H,s); 3.75(3H,s); 7.24-7.28(1H,m); 7.31-7.53(4H,m);7.48(1H,s); 7.62-7.69(2H,m); 8.12-8.15(1H,d); 8.65-8.68(1H,d);8.82(1H,s) ppm.

EXAMPLE 3

This Example illustrates the preparation of (E)-methyl2-[2-(6-(imidazol-1-yl)pyrimidin-4-yloxy)phenyl]-3-methoxypropenoate(Compound No. 8 of Table I).

To a stirred suspension of sodium hydride (0.65 g, 55% dispersion inoil, pre-washed with petrol) in dry DMF (5 ml) at 10°-15° C. undernitrogen, was added a solution of imidazole (1.02 g, 15 mmol) over fiveminutes. The reaction mixture effervesced and an exotherm took place.After stirring for 11/2 hours at room temperature, the cloudy solutionwas added drop-wise over one hour to a solution of4,6-dichloropyrimidine in dry DMF (10 ml) at 0° C. for one hour, addedto water and then extracted with ether (×3). The combined ether extractswere washed with dilute sodium hydroxide solution and water (×3) andthen dried. Concentration under reduced pressure gave4-chloro-6-(imidazol-1-yl)pyrimidine as a pale yellow solid (1.00 g);m.p. 122°-4° C., which was used without further purification.

A solution of 4-chloro-6-(imidazol-1-yl)pyrimidine (0.54 g, 3 mmol) indry DMF (5 ml) was added drop-wise over five minutes to sodiumthiomethoxide (0.23 g, 3.15 mmol) in dry DMF (5 ml) at 0° C. undernitrogen. After stirring at 0° C. for 45 minutes, the reaction mixturewas allowed to warm to room temperature. After two hours, the reactionmixture was poured into water and extracted with ether (×3). Thecombined ether extracts were washed with water, dried and evaporated togive a pale yellow solid (0.30 g). Chromatography on silicagel (eluentether) afforded 4-(imidazol-1-yl)-6-thiomethoxypyrimidine (0.08 g) as awhite solid, m.p. 123°-5° C. A second fraction (0.14 g) containing 88%of the desired product as a white solid was also isolated. Treatment ofthis material (0.14 g) with finely ground potassium permanganate (0.14g) in aqueous acetic acid (7.5 ml) at room temperature for two hoursafforded a brown solution which was left to stand overnight. Sulphurdioxide was passed through the solution until decolourisation had takenplace and the resulting solution was extracted with ethyl acetate (×2).The combined organic layers dried and evaporated to give a yellow gum(0.10 g). The gum was redissolved in dichloromethane, washed with sodiumbicarbonate solution and water (×2) and then dried and concentrated toafford crude 4-(imidazol-1-yl)-6-methanesulphonylpyrimidine (0.06 g),which was used without further purification.

A solution of crude 4-(imidazol-1-yl)-6-methanesulphonylpyrimidine (0.06g) in dry DMF (2 ml) was added over one minute to a stirred suspensionof (E)-methyl 2-(2-hydroxyphenyl)-3-methoxypropenoate (0.056 g) andpotassium carbonate (0.037 g) in DMF (3 ml) at 5° C. The reactionmixture was stirred at 5° C. for fifteen minutes and then allowed towarm to room temperature. After stirring overnight, the reaction mixturewas poured into water and extracted with ether (×4). The combinedextracts were washed with dilute sodium hydroxide solution (×2) andwater (×3) and then dried. Evaporation gave a colourless gum (0.05 g).Chromatography on silicagel (eluent ethyl acetate) afforded the titlecompound as a colourless gum (0.03 g); IR max. 1705, 1620 cm⁻¹

¹ H NMR (CDCl₃) δ3.59(3H,s); 4.74(3H,s); 6.66(1H,s); 7.19-7.46(5H,m);7.45(1H,s); 7.58(1H,m); 8.40(1H,s); 8.66(1H,s) ppm.

EXAMPLE 4

This Example illustrates the preparation of (E)-methyl2-[2-(6-(1,2,4-triazol-1-yl)pyrimidin-4-yloxy)phenyl]-3-methoxypropenoate(Compound No. 10 of Table I).

To a stirred suspension of sodium hydride (0.87 g, 55% dispersion inoil, pre-washed with petrol) in dry DMF (5 ml) under nitrogen at 10°-18°C. was added drop-wise a solution of 1,2,4-triazole (1.38, 20 mmol) indry DMF (10 ml) (effervescence). The reaction mixture was stirred atroom temperature for one hour, cooled to 0°-4° C. and then a solution of4,6-dichloropyrimidine (2.98 g, 20 mmol) in dry DMF (10 ml) addeddrop-wise over 45 minutes. The resulting reddish solution was stirredfor 90 minutes at 0° C. and then poured into water. A buff-colouredprecipitate (0.88 g) was formed, which was isolated by filtration andcharacterised as 4,6-di(1,2,4-triazol-1-yl)pyrimidine, m.p. 204°-208° C.The aqueous filtrate was extracted with ether (×3) and the combinedether extracts washed with brine and water (×2). The pale yellowsolution was dried and concentrated under reduced pressure to give apale cream-coloured solid (1.50 g), which was recrystallised fromdichloromethane-petrol to afford4-chloro-6-(1,2,4-triazol-1-yl)pyrimidine (1.08 g) as an off-whitesolid, m.p. 93°-7° C.

To a stirred suspension of sodium thiomethoxide (0.39 g, 1.05 equ.) indry DMF (5 ml) under nitrogen at 0° C. was added drop-wise over 15minutes a solution containing 4-chloro-6-(1,2,4-triazol-1-yl) in dry DMF(10 ml). After stirring at 0° C. for 90 minutes, the reaction mixturewas poured into water and extracted with ethyl acetate (×3). Thecombined organic extracts were washed with brine (×2), dried andevaporated to give a yellow solid (0.60 g). Chromatography on silicagel(eluent ether) gave 4-thiomethyl-6-(1,2,4-triazol-1-yl)pyrimidine (0.20g) as a white solid (85% pure by g.c) which was used in the next stagewithout further purification.

The product (0.20 g) was dissolved in glacial acetic acid (3.5 ml) at10°-15° C. and a solution of finely ground potassium permanganate (0.20g) in water (7 ml) added drop-wise over 15 minutes. The dark brownreaction mixture was stirred overnight at room temperature and thensulphur dioxide was passed through until decolourisation had takenplace. The aqueous solution was extracted with ethyl acetate and thecombined organic layers washed with aqueous sodium bicarbonate solution(×4) and water and then dried. The solvent was removed under reducedpressure to give a white gum (0.12 g). Trituration with ether afforded4-(methanesulphonyl)-6-(1,2,4-triazol-1-yl)pyrimidine (0.052 g) as asolid.

To a stirred suspension containing anhydrous potassium carbonate (28 mg)and (E)-methyl 2-(2'-hydroxyphenyl)-3-methoxypropenoate (43 mg) in dryDMF (3 ml) at 0° C. was added a solution of4-(methanesulphonyl)-6-(1,2,4-triazol-1-yl)pyrimidine (46 mg) in dry DMF(2 ml). The reaction mixture was stirred at 0°-2° C. for 20 minutes andthen allowed to warm to room temperature. After two hours, the reactionmixture was poured into water and extracted with ether (×4). Thecombined extracts were washed with dilute sodium hydroxide solution (×2)followed by water (×3) and then dried. Evaporation under reducedpressure gave a white foam (0.05 g) which was recrystallised fromdichloromethane-petrol to afford the title compound (37 mg) as whitesolid; m.p. 127°-8° C., IR max. 1692, 1625 cm⁻¹ ;

¹ H NMR (CDCl₃) δ3.60(3H,s); 3.75(3H,s); 7.20-7.44(5H,m); 7.46(1H,s);8.12(1H,s); 8.65(1H,s); 9.20(1H,s) ppm.

EXAMPLE 5

This Example illustrates the preparation of (E)-methyl2-[2-(6-(4-trifluoromethyl-6-oxopyrimidin-1-yl)pyrimidin-4-yloxy)phenyl]-3-methoxypropenoate(compound No. 31 of Table I).

To a stirred suspension of sodium hydride (0.14 g, 3.2 mmol, 55%dispersion in oil, pre-washed with n-hexane) in dry DMF (10 ml) wasadded drop-wise a solution of 4-hydroxy-6-trifluoromethylpyrimidine(0.50 g, 3.05 mmol) in dry DMF (6 ml). The mixture was stirred for afurther one hour until all evolution of hydrogen had ceased. To theresulting cloudy suspension was added a solution of (E)-methyl2-[2-(6-chloropyrimidin-4-yloxy)phenyl]-3-methoxypropenoate (0.98 g,3.05 mmol) in dry DMF (9 ml). After stirring at room temperature for onehour, a catalytic amount of copper(I) chloride was added and thereaction mixture heated over the weekend at 110° C. The brown reactionmixture was cooled, diluted with dichloromethane (30 ml) and filtered.The filter pad was washed with dichloromethane (2×15 ml) and thecombined filtrate washed with water (2×35 ml). An emulsion formed duringeach wash which could be broken up by filtration. The dichloromethanelayer was separated, treated with charcoal, dried and evaporated to givea dark brown oil (0.98 g). Chromatography on silica gel (eluentethylacetate-n-hexane, 5:2) gave the title compound as a gum whichcrystallised from ether-hexane as a cream-coloured solid (0.13 g, 9.5%);m.pt. 130°-1° C., infrared maxima 1718, 1700, 1629 cm⁻¹.

¹ H NMR (CDCl₃) δ3.62(3H,s); 3.76(3H,s); 6.92(1H,s); 7.19-7.52(4H,m);7.48(1H,s); 7.61(1H,s); 7.8(1H,s); 9.02(1H,s) ppm.

The following are examples of compositions suitable for agricultural andhorticultural proposes which can be formulated from the compounds of theinvention. Such compositions form another aspect of the invention.Percentages are by weight.

EXAMPLE 6

An emulsifiable concentrate is made up by mixing and stirring theingredients until all are dissolved.

    ______________________________________                                        Compound No. 18 of Table I                                                                            10%                                                   Benzyl alcohol          30%                                                   Calcium dodecylbenzenesulfphonate                                                                      5%                                                   Nonylphenolethoxylate (13 mole                                                                        10%                                                   ethylene oxide)                                                               Alkyl benzenes          45%                                                   ______________________________________                                    

EXAMPLE 7

The active ingredient is dissolved in methylene dichloride and theresultant liquid sprayed on to the granules of attapulgite clay. Thesolvent is then allowed to evaporate to produce a granular composition.

    ______________________________________                                        Compound No. 18 of Table I                                                                          5%                                                      Attapulgite granules 95%                                                      ______________________________________                                    

EXAMPLE 8

A composition suitable for use as a seed dressing is prepared bygrinding and mixing the three ingredients.

    ______________________________________                                        Compound No. 18 of Table I                                                                         50%                                                      Mineral oil           2%                                                      China clay           48%                                                      ______________________________________                                    

EXAMPLE 9

A dustable powder is prepared by grinding and mixing the activeingredient with talc.

    ______________________________________                                        Compound No. 18 of Table I                                                                          5%                                                      Talc                 95%                                                      ______________________________________                                    

EXAMPLE 10

A suspension concentrate is prepared by ball milling the ingredients toform an aqueous suspension of the ground mixture with water.

    ______________________________________                                        Compound No. 18 of Table I                                                                         40%                                                      Soidum lignosulphonate                                                                             10%                                                      Bentonite clay        1%                                                      Water                49%                                                      ______________________________________                                    

This formulation can be used as a spray by diluting into water orapplied directly to seed.

EXAMPLE 11

A wettable powder formulation is made by mixing together and grindingthe ingredients until all are throughly mixed.

    ______________________________________                                        Compound No. 18 of Table I                                                                         25%                                                      Sodium lauryl sulphate                                                                              2%                                                      Sodium lignosulphonate                                                                              5%                                                      Silica               25%                                                      China clay           43%                                                      ______________________________________                                    

EXAMPLE 12

The compounds were tested against a variety of foliar fungal diseases ofplants. The technique employed was as follows.

The plants were grown in John Innes Potting Compost (no 1 or 2) in 4 cmdiameter minipots. The test compounds were formulated either by beadmilling with aqueous Dispersol T or as a solution in acetone oracetone/ethanol which was diluted to the required concentrationimmediately before use. For the foliage diseases, the formulations (100ppm active ingredient) were sprayed onto the foliage and applied to theroots of the plants in the soil. Alternatively, the compounds wereapplied as a foliar spray only at a concentration of 10 ppm. The sprayswere applied to maximum retention and the root drenches to a finalconcentration equivalent to approximately 40 ppm a.i. in dry soil. Tween20, to give a final concentration of 0.05%, was added when the sprayswere applied to cereals.

For most of the tests the compound was applied to the soil (roots) andto the foliage (by spraying) one or two days before the plant wasinoculated with the disease. An exception was the test on Erysiphegraminis in which the plants were inoculated 24 hours before treatment.Foliar pathogens were applied by spray as spore suspensions onto theleaves of test plants. After inoculation, the plants were put into anappropriate environment to allow infection to proceed and then incubateduntil the disease was ready for assessment. The period betweeninoculation and assessment varied from four to fourteen days accordingto the disease and environment.

The disease control was recorded by the following grading:

4=no disease

3=trace-5% of disease on untreated plants

2=6-25% of disease on untreated plants

1=26-59% of disease on untreated plants

0=60-100% of disease on untreated plants.

The results are shown in Table IV.

                                      TABLE IV                                    __________________________________________________________________________                 PUCCINIA                                                                              ERYSIPHE                                                                             VENTURIA                                                                              PYRICULARIA                               COMPOUND                                                                              TABLE                                                                              RECONDITA                                                                             GRAMINIS                                                                             INAEQUALIS                                                                            ORYZAE                                    NO      NO   (WHEAT) (BARLEY)                                                                             (APPLE) (RICE)                                    __________________________________________________________________________     8      I    3.sup.a 0.sup.a                                                                              0.sup.a 0.sup.a                                   10      I    0.sup.a 0.sup.a                                                                              0.sup.a 0.sup.a                                   17      I    4       4      4       4                                         18      I    --      4      4       4                                         30      I    4.sup.a 4.sup.a                                                                              4.sup.a 3.sup.a                                   31      I    0.sup.a --     3.sup.a --                                        __________________________________________________________________________                                       PHYTOPHTHORA                                                CERCOSPORA                                                                              PLASMOPARA                                                                            INFESTANS                                  COMPOUND    TABLE                                                                              ARACHIDICOLA                                                                            VITICOLA                                                                              LYCOPERSICI                                NO          NO   (PEANUT)  (VINE)  (TOMATO)                                   __________________________________________________________________________     8          I    2.sup.a   0.sup.a 0.sup.a                                    10          I    2.sup.a   0.sup.a 0.sup.a                                    17          I    4         4       0                                          18          I    --        4       0                                          30          I    --        4.sup.a 4.sup.a                                    31          I    --        0.sup.a 0.sup.a                                    __________________________________________________________________________     .sup.a = 10 ppm foliar application only                                       -- = no result                                                           

We claim:
 1. A compound having the formula (I): ##STR104## in which anytwo of K, L and M are nitrogen and the other is CH; and X is anoptionally substituted 6-membered heterocyclic ring containing at leastone trivalent nitrogen atom by which it is attached to the centralpyrimidine ring; the heterocyclic ring being selected from the groupconsisting of pyrimidinone, pyrazinone, pyridazinone, 1,2,4-triazinone,1,3,5-triazinone and morpholine and the optional substituents beingselected from the group consisting of halogen, C₁₋₄ alkyl, C₃₋₆cycloalkyl, C₂₋₄ alkenyl, C₂₋₄ alkynyl, C₂₋₄ alkenyloxy, C₂₋₄alkynyloxy, phenyl, benzyloxy, cyano, isocyano, isothiocyanato, nitro,oxo, NR¹ R², NHCOR¹, NHCONR¹ R², NHSO₂ R¹, OR¹, OCOR¹, OSO₂ R¹, SR¹,SOR¹, SO₂ R¹, COR¹, CR¹ ═NOR², CO₂ R¹, CONR¹ R² and CSNR¹ R², wherein R¹and R² are independently hydrogen, C₁₋₄ alkyl or phenyl, and wherein thealiphatic moieties of any of the substituents are substituted with oneor more of halogen, cyano, OR¹ or OCOR¹ and the phenyl moieties of anyof the substituents being substituted with one or more of halogen, C₁₋₄alkyl, C₁₋₄ alkoxy, nitro or cyano; or any two substitutents, when orthoto one another, join to form a benzene ring which is optionallysubstituted with one or more of the substituents recited above for theoptionally substituted heterocyclic ring.
 2. A compound according toclaim 1 in which K and L are nitrogen, M is CH, and X is an optionallysubstituted heterocyclic ring selected from the group consisting ofpyrimidinone, pyrazinone, pyridazinone, 1,2,4-triazinone and1,3,5-triazinone.
 3. A compound according to claim 2 in which X is anoptionally substituted pyrimidinone.
 4. A compound according to claim 2in which X is an optionally substituted pyrazinone.
 5. A compoundaccording to claim 2 in which X is an optionally substitutedpyridazinone.
 6. A compound according to claim 2 in which X is anoptionally substituted 1,2,4-triazinone.
 7. A compound according toclaim 2 in which X is an optionally substituted 1,3,5-triazinone.
 8. Acompound according to claim 6 (E)-methyl2-[-(6-(4-trifluoromethyl-6-oxopyrimidin-1-yl)pyrimidin-4-yloxy)phenyl]-3-methoxy-propenoate.9. A fungicidal composition comprising a fungicidally effective amountof a compound according to claim 1 and a fungicidally acceptable carrieror diluent therefor.
 10. A method of combating fungi which comprisesapplying to plants, to the seeds of plants or to the locus of the plantsor seeds, a compound according to claim 1 or a composition according toclaim 9.